EP1549605B1 - Verfahren zur herstellung von alkenylcarboxylaten - Google Patents

Verfahren zur herstellung von alkenylcarboxylaten Download PDF

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EP1549605B1
EP1549605B1 EP03753709A EP03753709A EP1549605B1 EP 1549605 B1 EP1549605 B1 EP 1549605B1 EP 03753709 A EP03753709 A EP 03753709A EP 03753709 A EP03753709 A EP 03753709A EP 1549605 B1 EP1549605 B1 EP 1549605B1
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Prior art keywords
catalyst
alkene
oxygen
reaction zone
carboxylic acid
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French (fr)
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EP1549605A1 (de
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Evert Jan Ditzel
Simon Frederick Thomas Froom
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Ineos Commercial Services UK Ltd
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Ineos Commercial Services UK Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/04—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds
    • C07C67/05—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds with oxidation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/04—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds
    • C07C67/05—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds with oxidation
    • C07C67/055—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds with oxidation in the presence of platinum group metals or their compounds

Definitions

  • the present invention relates to a process for the production of alkenyl carboxylates, and, in particular to a process for the production of vinyl acetate.
  • Vinyl acetate is generally prepared commercially by contacting ethylene and acetic acid with molecular oxygen in the presence of a catalyst active for the production of vinyl acetate.
  • the process may be carried out in either a fixed bed or a fluid bed reactor.
  • a process employing a fixed catalyst bed is described, for example, in EP-A-0845453 .
  • Processes employing a fluidised catalyst bed are described, for example, in EP-A-0672453 , EP-A-0685449 , EP-A-0685451 , EP-A-0985655 and EP-A-1008385 .
  • EP-A-0 672 453 describes a process for the fluid bed production of vinyl acetate from ethylene, acetic acid and a molecular oxygen-containing gas in the presence of a promoted palladium catalyst.
  • Catalysts active for the production of vinyl acetate may typically comprise a Group VIII metal, such as palladium; a co-promoter, such as gold, copper, cerium or mixtures thereof; and, optionally, a co-promoter, such as potassium acetate.
  • a Group VIII metal such as palladium
  • co-promoter such as gold, copper, cerium or mixtures thereof
  • co-promoter such as potassium acetate.
  • catalysts active for the production of vinyl acetate are described in GB 1 559 540 ; US 5,185,308 and EP-A-0672453 .
  • EP-A-0672453 describes palladium containing catalysts and their preparation for fluid bed vinyl acetate processes.
  • a commercial vinyl acetate process is generally operated as a continuous process. Ideally, the vinyl acetate process is started up smoothly. However, numerous problems (process upsets) can occur during both the start-up and operation of the process. In addition to any process upsets, a commercial vinyl acetate process also has planned shut-downs, for example, for the periodic maintenance of the plant and/or replacement of deactivated catalyst with fresh catalyst.
  • the molecular oxygen-containing gas feed to the reaction zone is usually shut-off.
  • the catalyst will be exposed to ethylene in the substantial absence of molecular oxygen.
  • the molecular oxygen-containing gas feed to the reaction zone is shut-off prior to shutting-off the acetic acid feed. The catalyst will then be left exposed to ethylene in the substantial absence of molecular oxygen.
  • molecular oxygen introduced in to the reactor on starting-up or of restarting the process may not be consumed thereby creating an accumulation of unreacted molecular oxygen in the reactor and increasing the risk of explosion.
  • a fluid bed process for the production of an alkenyl carboxylate by reacting an alkene, a carboxylic acid and a molecular oxygen-containing gas in a reaction zone in the presence of a catalyst comprising palladium, a promoter and optionally a co-promoter at an elevated temperature, T, to produce an outlet stream from the reaction zone comprising alkenyl carboxylate and oxygen, characterised in that, where during a process upset or shut-down the catalyst is exposed to the alkene at a partial pressure, P, in the presence or absence of the carboxylic acid and the outlet stream comprises less than 2 vol% oxygen, then the partial pressure, P, of the alkene is reduced to at least 50% less than P and/or the reaction temperature is reduced to below 100°C, so as to suppress formation of benzene and/or suppress the inhibition of the catalyst, the period of time, Z, during which the catalyst is exposed to the alkene in the presence or absence of the carboxylic acid and at oxygen levels of less than
  • the partial pressure of alkene, P, such as ethylene, in the reaction zone is at least 0.3 bar or greater, such as at least 1 bar, for example, at least 2 bar.
  • the partial pressure of alkene in the reaction zone is reduced to at least 50% less than P.
  • P is at least 2 bar, and the partial pressure of alkene in the reaction zone is reduced to less than 1 bar.
  • the partial pressure of alkene in the reaction zone is reduced to approximately 0 bar by removing substantially all the alkene from the reaction zone when low levels of molecular oxygen are present.
  • reducing the partial pressure of alkene comprises removing all reactant gases (i.e. alkene, optional carboxylic acid, and any oxygen present) from the reaction zone, for example by purging the reaction zone with an inert gas, such as nitrogen.
  • the reaction is typically carried out at a temperature, T, of at least 100°C, such as at least 140°C.
  • the reaction temperature is reduced to below 100°C, such as to 50°C or lower, for example, to ambient temperature, such as approximately 20°C.
  • the concentration of oxygen in the outlet stream from the reaction zone is greater than 2vol%.
  • the concentration of oxygen in the outlet stream may be at a low level, that is less than 2vol%, such as 0 to 0.5 vol% or 0 to 0.2 vol%.
  • the amount of benzene produced on exposure of the catalyst to the alkene in the presence of low levels of oxygen will vary, depending on, for example, the exact oxygen concentration in the outlet stream, the reaction temperature, the specific catalyst used, the alkene partial pressure and the total reaction pressure. In addition, the amount of benzene produced will depend on the period of time for which the catalyst is exposed to the alkene in the presence of low levels of oxygen.
  • the catalyst will be exposed to an alkene (and optionally carboxylic acid) in the presence of low levels of oxygen for a period of time (period of contact), Z, before the partial pressure of the alkene and/or the reaction temperature are reduced.
  • a period of contact Z
  • the period of contact, Z should be minimized.
  • Benzene formation may be determined by any suitable method known in the art, for example, such as gas chromatography and/or mass spectrometry.
  • the amount of benzene produced may be measured, for example, in the outlet stream directly at the outlet of the reaction zone and/or at a point downstream of the outlet from the reaction zone, such as in the final vinyl acetate product.
  • the activity of a catalyst may be determined by any suitable method known in the art, for example, by analysis of the amount of product produced using a suitable analytical techniques, such as gas chromatography and/or mass spectrometry.
  • a suitable analytical techniques such as gas chromatography and/or mass spectrometry.
  • the production rate of vinyl acetate is suitably determined by calculating the amount of vinyl acetate product produced per unit catalyst per unit time.
  • the space-time yield may be measured as the production of vinyl acetate in grammes of vinyl acetate produced per kilogram of catalyst per hour (gVA/kg-cat/hr).
  • the exact degree of inhibition of the catalyst may also be dependent upon factors other than the oxygen concentration and the period of contact, Z, such as the specific nature of the catalyst employed, the sensitivity of the catalyst to the alkene and carboxylic acid, the nature of the reactant(s) to which the catalyst is exposed and their partial pressures, and also the reaction temperature. Generally, however, the period of contact, Z, between the catalyst and alkene (and optionally carboxylic acid) in the substantial absence of oxygen should be minimized.
  • the period of contact, Z, of the catalyst with ethylene or ethylene and acetic acid, in the substantial absence of molecular oxygen is in the range [>0 to 12] hours and preferably, in the range [>0 to 6] hours.
  • Inhibition of the catalyst may be greater where the catalyst is exposed to both alkene and carboxylic acid, in the substantial absence of molecular oxygen.
  • the period of contact is preferably less than the period of contact with alkene alone.
  • the period of contact, Z is in the range [>0 to 12] hours, preferably, in the range [>0 to 6] hours.
  • Catalyst inhibition may also be at least partially mitigated by reducing the partial pressure of carboxylic acid in the reaction zone, even if the partial pressure of alkene is not reduced or the reaction temperature is not reduced.
  • Catalyst inhibition may also be at least partially mitigated by reducing the partial pressure of carboxylic acid in the reaction zone, even if the partial pressure of alkene is not reduced or the reaction temperature is not reduced.
  • the partial pressure of alkene is reduced and/or the temperature is reduced.
  • fluid bed processes may be run at higher nominal molecular oxygen levels in the reaction zone than in fixed bed processes.
  • composition by percentage Unless otherwise stated all measurements of composition by percentage throughout this specification are measurements in terms of percentage by volume.
  • the volume of molecular oxygen in the outlet stream from the reaction zone, as used herein, is measured on a "dry-gas" basis i.e. after removal of condensables that may be present in the outlet stream at the exit of the reaction zone.
  • alkenyl carboxylate such as vinyl acetate
  • the production of alkenyl carboxylate is carried out heterogeneously with the reactants being present in the gas phase or as a mixture of gas and liquid phases.
  • the process of the present invention may be carried out as a fixed bed or a fluid bed process, preferably, a fluid bed process.
  • the alkene may be any suitable alkene or a mixture of alkenes, but is preferably a C 2 -C 4 alkene, such as ethylene.
  • the alkene may be fed in substantially pure form or admixed with other materials, such as, for example, other alkenes or hydrocarbons, hydrogen or inert materials.
  • the alkene is ethylene
  • the ethylene may be fed in substantially pure form or may be fed admixed with one or more of nitrogen, methane, ethane, carbon dioxide, water in the form of steam, hydrogen and C 3 /C 4 alkenes or alkanes.
  • the alkene may comprise fresh and/or recycle alkene.
  • the fresh and recycle alkene for example, ethylene
  • the fresh and recycle alkene may be introduced into the reaction zone either as separate feed streams or as a single feed stream comprising both fresh and recycle alkene.
  • the carboxylic acid may be any carboxylic acid or a mixture of carboxylic acids, but is preferably a C 2 -C 4 carboxylic acid, such as acetic acid.
  • alkenyl carboxylates that may be produced in the process of the present invention include vinyl propionate, allyl acetate and allyl propionate.
  • the carboxylic acid used in the process of the present invention is acetic acid, such that the alkenyl carboxylate produced is vinyl acetate.
  • the carboxylic acid may be introduced into the reaction zone in liquid form or in vapour form. Where the process is a fixed bed process then the carboxylic acid is preferably introduced in to the reaction zone in vapour form. Where the process is a fluid bed process then the carboxylic acid is preferably introduced in to the reaction zone as a liquid spray.
  • the carboxylic acid may comprise fresh and/or recycle acid.
  • the fresh and recycle carboxylic acid may be introduced into the reaction zone either as separate feed streams or as a single feed stream comprising both fresh and recycle acid.
  • the carboxylic acid may comprise at least a portion of the acid obtained from downstream processes such as from the separation of the acid from a mixture of the acid/alkenyl carboxylate/water.
  • the molecular oxygen-containing gas may be any suitable gas containing molecular oxygen and may suitably be air or a gas richer or poorer in molecular oxygen than air.
  • a suitable molecular oxygen-containing gas may be, for example, oxygen diluted with a suitable diluent, for example nitrogen, argon or carbon dioxide.
  • the molecular oxygen-containing gas is essentially pure oxygen.
  • the alkene, carboxylic acid and molecular oxygen-containing gas may be introduced into the reaction zone in any suitable proportions for the production of the alkenyl carboxylate.
  • the alkene may be present in the feed to the reaction zone in a range between 30 and 85mol% of the total reaction composition, preferably at least 50mol%, such as in an amount of at least 60mol% of the total reaction composition.
  • the carboxylic acid may be present in the feed to the reaction zone in a range between 2 and 30mol% of the total reaction composition, preferably 5 to 15mol%.
  • the amount of molecular oxygen-containing gas present in the feed to the reaction zone is controlled by flammability constraints. .
  • the molecular oxygen-containing gas is preferably added directly to the reaction zone and the oxygen may be present at a higher level, for example, in a range 3 to 20 mol% of the total reaction composition.
  • a balance of an inert gas, preferably one or more of nitrogen, carbon dioxide and argon may also be present in the reactant feed.
  • the catalyst for use in the process of the present invention may be any promoted Group VIII metal suitable for the production of an alkenyl carboxylate from an alkene, carboxylic acid and a molecular oxygen-containing gas.
  • the catalyst suitable for use in the production of vinyl acetate in a fixed bed process may comprise any suitable catalyst known in the art, for example, as described in GB 1 559 540 and US 5,185,308 .
  • GB 1 559 540 describes a catalyst active for the preparation of vinyl acetate by the reaction of ethylene, acetic acid and molecular oxygen, the catalyst consisting essentially of:
  • a catalyst suitable for use in the production of vinyl acetate in a fluid bed process may comprise a Group VIII metal, a catalyst promoter and an optional co-promoter.
  • the preferred metal is palladium.
  • Suitable sources of palladium include palladium (II) chloride, sodium or potassium tetrachloropalladate, (II), (Na 2 PdCl 4 or K 2 PdCl 4 ), palladium acetate, palladium (II) nitrate or palladium (II) sulphate.
  • the metal may be present in a concentration of greater than 0.2% by weight, preferably greater than 0.5% by weight based upon total weight of catalyst. The metal concentration may be as high as 10% by weight. Generally, the higher the active metal loading in a catalyst suitable for use in vinyl acetate production, the more catalytically active it will be.
  • the catalyst for the production of vinyl acetate comprises a promoter.
  • Suitable promoters include gold, copper, cerium or mixtures thereof.
  • a preferred promoter is gold.
  • Suitable sources of gold include gold chloride, tetrachloroauric acid (HAuCl 4 ), NaAuCl 4 , KAuCl 4 , dimethyl gold acetate, barium acetoaurate or gold acetate.
  • the preferred gold compound is HAuCl 4 .
  • the promoter metal may be present in an amount of from 0.1 to 10% by weight in the finished catalyst.
  • the catalyst suitable for use in the production of vinyl acetate may also comprise a co-promoter material.
  • Suitable co-promoters include Group I, Group II, lanthanide or transition metals, for example cadmium, barium, potassium, sodium, manganese, antimony, and/or lanthanum, which are present in the finished catalyst as salts, e.g. an acetate salt.
  • the preferred salts are potassium or sodium acetate.
  • the co-promoter is preferably present in the catalyst composition in a concentration of 0.1 to 15% by weight of catalyst, more preferably, from 1 to 5% by weight.
  • the preferred concentration of co-promoter salt is up to 6% by weight, especially 2.5 to 5.5%.
  • the acid is introduced in the vapour phase the co-promoter salt is preferably present in a concentration up to 11 wt%.
  • the catalyst may be a supported catalyst.
  • Suitable catalyst supports include porous silica, alumina, silica/alumina, titania, silica/titania or zirconia.
  • the support is preferably silica, and, suitably, the support may have a pore volume from 0.2 to 3.5 ml per gram of support, a surface area of 5 to 800 m 2 per gram of support and an apparent bulk density of 0.3 to 1.5 g/ml.
  • the particles of the catalyst are maintained in a fluidised state by a suitable gas flow through the system. Excess flow rate may cause channeling of the gas through the reactor which decreases conversion efficiency.
  • a typical catalyst useful in the production of vinyl acetate in a fluidised bed reaction may have the following particle size distribution:- 0 to 20 microns 0-30 wt% 20 to 44 microns 0-60 wt% 44 to 88 microns 10-80 wt% 88 to 106 microns 0-80 wt% >106 microns 0-40 wt% >300 microns 0-5 wt%
  • support particles sizes of 44, 88, 106 and 300 microns are arbitrary measures in that they are based on standard sieve sizes. Particle sizes and particle size distributions may be measured by an automated laser device such as a Microtrac X100.
  • the catalyst may be prepared by any suitable method.
  • the catalyst for the production of vinyl acetate may be prepared by the method detailed in EP-A-0672453 .
  • the method of catalyst preparation may be varied to optimise catalyst performance based on maximising yield and selectivity.
  • the process of the present invention may be carried out at a temperature in the reaction zone, T, from 100 to 400°C and at atmospheric or at greater than atmospheric pressure, for example, at up to 20 barg.
  • the process for the production of vinyl acetate when carried out in a fluid bed reaction zone may suitably be operated at a temperature from 100 to 400°C, preferably 140 to 210°C and a pressure of 1 x 10 5 to 2 x 10 6 Pa gauge (1 to 20 barg), preferably 6 x 10 5 to 1.5 x 10 6 Pa gauge (6 to 15 barg), especially 7 x 10 5 to 1.2 x 10 6 Pa gauge (7 to 12 barg).
  • the process for the production of vinyl acetate when carried out in a fixed bed reaction zone may suitably be operated at a temperature from 100 to 400°C, preferably 140 to 180°C and a pressure of 1 x 10 5 to 2 x 10 6 Pa gauge (1 to 20 barg), preferably 6 x 10 5 to 1.5 x 10 6 Pa gauge (6 to 15 barg), especially 7 x 10 5 to 1.2 x 10 6 Pa gauge (7 to 12 barg).
  • a 1.8g sample of a promoted palladium vinyl acetate catalyst was mixed with 20-22g of inert diluent, and contacted for a period of 18, 66 or 138 hours with either ethylene or a mixture of ethylene and acetic acid, at 160°C and 8 barg in a fluidised bed microreactor.
  • the flow rates of ethylene and acetic acid were 0.49 mol/hr and 0.05 mol/hr respectively.
  • the fluidised bed microreactor had a diameter of 1" and was fitted with baffle trays. Gas flow was provided through a plenum at the base of the unit, and also from a small sparger mounted within the fluid bed.
  • each catalyst was tested in the fluidised bed microreactor operated at 160°C and 8 bar.
  • a reaction mixture of 52mol% ethylene, 5mol% acetic acid and 1.9mol% oxygen, with a nitrogen balance at a total flow rate of 0.93 mol/hr was fed into the reactor.
  • Samples were removed periodically and vinyl acetate was measured by gas chromatography (GC).
  • FIGs. 1 and 2 show the activity profile (space time yield (STY) in gVA/Kg-cat/hr) for a fresh, non pre-treated catalyst (catalyst 1) compared to equivalent catalysts (2 and 3) that have been pre-treated by exposure to ethylene and a mixture of ethylene and acetic acid respectively for 138 hours. It can be seen that both catalysts 2 and 3 have a significantly reduced initial activity compared to the non-pretreated catalyst. With time on stream the catalysts start to regain some of the lost activity.
  • STY space time yield
  • Figure 2 shows a comparison of the non pre-treated catalyst (catalyst 1, as above) with catalysts that have been pre-treated in a mixture of ethylene and acetic acid for two different periods of time, namely 18 hours (catalyst 4) and 138 hours (catalyst 3, as above) respectively.
  • the initial extent of catalyst inhibition is related to the length of time for which the catalyst was exposed to the mixture of ethylene and acetic acid.
  • the reactor was purged with nitrogen for 1 hour.
  • a feed comprising 60 mol% ethylene, 12 mol% acetic acid, 6.8 mol% oxygen, balance nitrogen was then fed into the reactor.
  • the oxygen flow in to the reactor was recorded in grammes per hour (g/hr) using a mass flow controller.
  • the oxygen level in the stream exiting the reactor was measured using a Servomex oxygen analyser, which reported in weight percent (wt%).
  • Figure 3 shows the oxygen levels exiting the reactor for pre-treated catalysts 5 to 9 compared to the oxygen level in the feed to the reactor. Varying levels of inhibition can be observed based on the time taken for the oxygen levels in the outlet to decrease relative to the oxygen feed level, denoting oxygen conversion.
  • catalyst 7 pre-treated with ethylene, acetic acid and nitrogen was the most inhibited, and was more inhibited than a catalyst pre-treated with ethylene and nitrogen alone (catalysts 6 and 9).
  • the nitrogen purge used on catalyst 6 before start-up appeared to make little difference to the inhibition of this catalyst compared to catalyst 9 which had had the same pre-treatment with ethylene and nitrogen, but without the subsequent nitrogen purge.
  • a fluidised bed reactor was operated with varying levels of oxygen in the product stream exiting from the reactor.
  • the reactor was operated at a temperature of approximately 155°C, and at a pressure of approximately 7.5 barg.
  • the feed to the reactor comprised ethylene, acetic acid and 3.5mol% oxygen.
  • the oxygen conversion was adjusted to give an oxygen concentration in the reactor exit stream within the range of approximately 0.2 to 2.5 vol%.
  • the oxygen concentration of the reactor exit stream was measured as an average over a 24 hour period prior to taking a sample of the stream for benzene analysis.

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Claims (22)

  1. Wirbelschichtverfahren zur Herstellung eines Alkenylcarboxylats durch Umsetzen eines Alkens, einer Carbonsäure und eines molekularen Sauerstoff enthaltenden Gases in einer Reaktionszone in Gegenwart eines Katalysators, der Palladium, einen Promotor und gegebenenfalls einen Copromotor umfasst, bei einer erhöhten Reaktionstemperatur T, wobei ein Auslassstrom aus der Reaktionszone, der Alkenylcarboxylat und Sauerstoff umfasst, entsteht, dadurch gekennzeichnet, dass dann, wenn der Katalysator während des Hochfahrens oder Herunterfahrens des Verfahrens dem Alken unter einem Partialdruck P in Anwesenheit oder Abwesenheit der Carbonsäure ausgesetzt ist und der Auslassstrom weniger als 2 Vol.-% Sauerstoff umfasst, der Partialdruck P des Alkens auf wenigstens 50% weniger als P reduziert wird und/oder die Reaktionstemperatur auf unter 100 °C reduziert wird, um die Bildung von Benzol zu unterdrücken und/oder die Hemmung des Katalysators zu unterdrücken, wobei die Zeitdauer Z, während der der Katalysator dem Alken in Anwesenheit oder Abwesenheit der Carbonsäure und bei Sauerstoffkonzentrationen von weniger als 2 Vol.-% Sauerstoff ausgesetzt ist, bevor der Partialdruck des Alkens auf wenigstens 50% weniger als P reduziert wird und/oder die Reaktionstemperatur auf unter 100 °C reduziert wird, im Bereich von >0 bis 12 Stunden liegt.
  2. Verfahren gemäß Anspruch 1, wobei der Katalysator in Gegenwart der Carbonsäure mit dem Alken in Kontakt gebracht wird.
  3. Verfahren gemäß Anspruch 1 oder 2, wobei der Auslassstrom 0 bis 0,5 Vol.-% Sauerstoff umfasst.
  4. Verfahren gemäß Anspruch 3, wobei der Auslassstrom 0 bis 0,2 Vol.-% Sauerstoff umfasst.
  5. Verfahren gemäß einem der vorstehenden Ansprüche, wobei der Partialdruck P des Alkens in der Reaktionszone wenigstens 1 bar beträgt.
  6. Verfahren gemäß Anspruch 1, wobei der Partialdruck des Alkens in der Reaktionszone dadurch reduziert wird, dass man im Wesentlichen das ganze Alken aus der Reaktionszone entfernt.
  7. Verfahren gemäß Anspruch 6, wobei das Alken, die optionale Carbonsäure und gegebenenfalls vorhandener Sauerstoff dadurch aus der Reaktionszone entfernt werden, dass man die Reaktionszone mit einem Inertgas, vorzugsweise Stickstoff, spült.
  8. Verfahren gemäß einem der vorstehenden Ansprüche, wobei die Reaktion bei einer Temperatur von wenigstens 140 °C durchgeführt wird.
  9. Verfahren gemäß einem der vorstehenden Ansprüche, wobei die Reaktionstemperatur auf wenigstens 50 °C unter T reduziert wird.
  10. Verfahren gemäß Anspruch 9, wobei die Reaktionstemperatur auf 50 °C oder darunter reduziert wird.
  11. Verfahren gemäß einem der vorstehenden Ansprüche, wobei der Katalysator >0 bis 6 Stunden lang bei geringen Konzentrationen von molekularem Sauerstoff mit dem Alken und gegebenenfalls der Carbonsäure in Kontakt steht, bevor man den Partialdruck des Alkens reduziert und/oder die Reaktionstemperatur reduziert.
  12. Verfahren gemäß einem der vorstehenden Ansprüche, wobei das Verfahren zur Herstellung des Alkenylcarboxylats heterogen durchgeführt wird, wobei die Reaktanten in der Gasphase oder als Gemisch von Gas- und flüssigen Phasen vorliegen.
  13. Verfahren gemäß einem der vorstehenden Ansprüche, wobei das Alken ein C2-C4-Alken ist.
  14. Verfahren gemäß einem der vorstehenden Ansprüche, wobei die Carbonsäure eine C2-C4-Carbonsäure ist.
  15. Verfahren gemäß einem der vorstehenden Ansprüche, wobei das Alken im Zustrom zur Reaktionszone in einem Bereich zwischen 30 und 85 Mol-% der gesamten Reaktionszusammensetzung vorhanden ist.
  16. Verfahren gemäß einem der vorstehenden Ansprüche, wobei die Carbonsäure im Zustrom zur Reaktionszone in einem Bereich zwischen 2 und 30 Mol-% der gesamten Reaktionszusammensetzung vorhanden ist.
  17. Verfahren gemäß einem der vorstehenden Ansprüche, wobei es sich bei dem molekularen Sauerstoff enthaltenden Gas um molekularen Sauerstoff handelt.
  18. Verfahren gemäß Anspruch 17, wobei das molekularen Sauerstoff enthaltende Gas im Zustrom zur Reaktionszone in einer Menge im Bereich von 3 bis 20 Mol-% der gesamten Reaktionszusammensetzung vorhanden ist.
  19. Verfahren gemäß einem der vorstehenden Ansprüche, wobei es sich bei dem Alken um Ethylen und bei der Carbonsäure um Essigsäure handelt, so dass es sich bei dem hergestellten Alkenylcarboxylat um Vinylacetat handelt.
  20. Verfahren gemäß einem der vorstehenden Ansprüche, wobei der Katalysator zur Verwendung in dem Verfahren zur Herstellung des Alkenylcarboxylats Palladium, einen Promotor, der aus Gold, Kupfer, Cer und Gemischen davon ausgewählt ist, und ein Copromotormaterial, das aus Cadmium, Barium, Kalium, Natrium, Mangan, Antimon und/oder Lanthan ausgewählt ist und als Salz in dem fertigen Katalysator vorhanden ist, umfasst.
  21. Verfahren gemäß Anspruch 20, wobei sich der Katalysator auf einem Katalysatorträger befindet, der aus porösem Siliciumoxid, Aluminiumoxid, Siliciumoxid/Aluminiumoxid, Titanoxid, Siliciumoxid/Titanoxid und Zirconiumoxid ausgewählt ist.
  22. Verfahren gemäß einem der vorstehenden Ansprüche, wobei die Temperatur T in der Reaktionszone im Bereich von 100 °C bis 400 °C liegt und der Druck in der Reaktionszone von Atmosphärendruck bis zu 20 bar Manometerdruck beträgt.
EP03753709A 2002-10-07 2003-09-29 Verfahren zur herstellung von alkenylcarboxylaten Expired - Lifetime EP1549605B1 (de)

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Application Number Priority Date Filing Date Title
GB0223215 2002-10-07
GBGB0223215.5A GB0223215D0 (en) 2002-10-07 2002-10-07 Processs
PCT/GB2003/004220 WO2004031120A1 (en) 2002-10-07 2003-09-29 Process for the production of alkenyl carboxylates

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EP1549605A1 EP1549605A1 (de) 2005-07-06
EP1549605B1 true EP1549605B1 (de) 2012-08-08

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JP (1) JP4933047B2 (de)
KR (1) KR101131028B1 (de)
CN (1) CN100577627C (de)
AU (1) AU2003271871A1 (de)
BR (1) BR0315131A (de)
CA (1) CA2497802A1 (de)
ES (1) ES2388663T3 (de)
GB (1) GB0223215D0 (de)
MX (1) MXPA05003676A (de)
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WO (1) WO2004031120A1 (de)

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FR2934264B1 (fr) * 2008-07-22 2012-07-20 Arkema France Fabrication d'esters de vinyle a partir de matieres renouvelables, esters de vinyle obtenus et utilisations
DE102010001097A1 (de) * 2010-01-21 2011-07-28 Wacker Chemie AG, 81737 Verfahren zur Herstellung von Vinylacetat
EP3831803B1 (de) * 2018-07-27 2024-09-04 Kuraray Co., Ltd. Verfahren zur herstellung von 1,3-bisacyloxy-2-methylen-propan
CN110746296A (zh) * 2019-11-12 2020-02-04 云南正邦科技有限公司 一种用微通道反应器制备乙酸乙烯酯的方法

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ES2135006T3 (es) * 1994-06-02 1999-10-16 Standard Oil Co Ohio Procedimiento en lecho fluido para la acetoxilacion de etileno en la produccion de acetato de vinilo.
GB9826754D0 (en) * 1998-12-04 1999-01-27 Bp Chem Int Ltd Process for the production of vinyl acetate

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CN1684938A (zh) 2005-10-19
GB0223215D0 (en) 2002-11-13
KR20050071550A (ko) 2005-07-07
JP2006502199A (ja) 2006-01-19
US7534910B2 (en) 2009-05-19
CN100577627C (zh) 2010-01-06
BR0315131A (pt) 2005-08-16
US20060167306A1 (en) 2006-07-27
ES2388663T3 (es) 2012-10-17
EP1549605A1 (de) 2005-07-06
WO2004031120A1 (en) 2004-04-15
JP4933047B2 (ja) 2012-05-16
TW200413309A (en) 2004-08-01
AU2003271871A1 (en) 2004-04-23
TWI314926B (en) 2009-09-21
KR101131028B1 (ko) 2012-03-29
MXPA05003676A (es) 2005-06-08
CA2497802A1 (en) 2004-04-15

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